1,2-Dichlorobenzene → HCID 118377934, compound

HRID 1055527Notes

Reaction equation

HRID 1055527 reaction equation
[C:1](=[O:58])([O:6][CH:7]([C@:9]12[O:16][C@:13]([C:17]3[CH:22]=[CH:21][C:20]([Cl:23])=[C:19]([CH2:24][C:25]4[CH:30]=[CH:29][C:28]([O:31][CH2:32][CH3:33])=[CH:27][CH:26]=4)[CH:18]=3)([O:14][CH2:15]1)[C@H:12]([O:34]CC1C=CC=CC=1)[C@@H:11]([O:42]CC1C=CC=CC=1)[CH:10]2[O:50]CC1C=CC=CC=1)[CH3:8])[O:2][CH:3]([CH3:5])[CH3:4].ClC1C=CC=CC=1Cl>[Pd].CO.O1CCCC1>[C:1](=[O:58])([O:2][CH:3]([CH3:5])[CH3:4])[O:6][CH:7]([C@:9]12[O:16][C@:13]([C:17]3[CH:22]=[CH:21][C:20]([Cl:23])=[C:19]([CH2:24][C:25]4[CH:30]=[CH:29][C:28]([O:31][CH2:32][CH3:33])=[CH:27][CH:26]=4)[CH:18]=3)([O:14][CH2:15]1)[C@H:12]([OH:34])[C@@H:11]([OH:42])[CH:10]2[OH:50])[CH3:8]

Participants

5

Reactant 2

HCID 72391,2-DichlorobenzeneHCID 118377831HCID 118377831, compound

Product 1

HCID 118377934HCID 118377934, compoundYield 74.5%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 21899815MeOH tetrahydrofuranSolvent

Procedure

To a solution of isopropyl 1-[(1R,3S,4R,5S)-2,3,4-tribenzyloxy-5-[4-chloro-3-[(4-ethoxyphenyl) methyl]phenyl]-6,8-dioxabicyclo[3.2.1]octan-1-yl]ethyl carbonate 13a (244 mg, 0.3 mmol) in a methanol/tetrahydrofuran mixture (v/v=4/1, 10 mL) were added o-dichlorobenzene (0.16 mL, 1.5 mmol) and 10% Pd/C (36 mg, 0.03 mmol) in turn at room temperature. The mixture was stirred at room temperature under H2 for 4 hours and filtered. The filtrate was concentrated in vacuo. The residue was purified by silica gel chromatography eluted with PE/EtOAc(v/v)=4/1 to give the title compound 13 as a white solid (120 mg, 75.0%, HPLC: 92.3%). The compound was characterized by the following spectroscopic data: MS (ESI, pos. ion) m/z: 537.3[M+H]+; and 1H NMR (600 MHz, DMSO-d6) δ(ppm): 7.40 (m, 2H), 7.29 (m, 1H), 7.11 (d, 2H), 6.84 (m, 2H), 5.58 (brs, 1H), 5.04 (brs, 2H), 4.93 (m, 1H), 4.73 (m, 1H), 4.50-3.98 (m, 5H), 3.54 (m, 2H), 3.44 (m, 2H), 1.31 (m, 6H), 1.23-1.20 (m, 6H).

Workup

  1. filtrationfiltered
  2. concentrationThe filtrate was concentrated in vacuo
  3. customThe residue was purified by silica gel chromatography
  4. washeluted with PE/EtOAc(v/v)=4/1

Sources & evidence

ORD record
ord-ff75e61b5ba34b4ea3dddeab0b1ded4c
Source dataset
uspto-grants-2016_07
Patent number
US09394329B2

Reaction notes

Loading…